Polyesters

ABSTRACT

THE POLYMERS OF THIS INVENTION ARE MADE BY FIRST REACTING AN ANHYDRIDE WITH A POLYOL, AND THEN REACTING THE PRODUCT WITH A HYDROXYL TERMINATED POLYESTER. THE POLYMERS ARE USEFUL AS FILM-FORMERS IN COATING COMPSOTIONS.

United States Patent Oflice' 3,704,255

Patented Nov. 28, 1972 UTILITY izgg The polymers of the invention areuseful as film- Robert Bram, Rochester, NY. assign to L du formers incoating compositions, particularly when com- Pont de Nemours andCompany, Wilmington, Del. 5 binFd with a Second Pf' y havingcomplementary N Drawing. Continuation-impart of abandoned applicaactlvegroups. Illustrative of such second polymers are tion Ser. No. 776,824,Nov. 18, 1968. This application heat reactive phenolics, polyglycidylethers and esters,

Mar. 3, 1971, Ser. No. 120,775 polyisocyanate resins, butylatedurea/formaldehyde C (307C 69/ 7 (303$ 17/02 resins andmelamine/formaldehyde/alkanol resins. Clams The polymers of theinvention can be used as film- V 10 formers by mixing from about 55 toabout 95 parts of the polymer with from about 5 to 45 parts of thesecond ABSTRACT OF THE DISCLOSURE complementary polymer, in a suitablesolvent. This so- The polymers of this invention are made by firstrelution can then be used directly to give clear coatings or acting ananhydride with a polyol, and then reacting it may be pigmented asdesired. the product with a hydroxyl terminated polyester. The Thecoating composition can be applied conventionally polymers are useful asfilm-formers in coating comand preferably is then baked for from about10 to 30 positions. minutes at 80-200 C.

The polymers of the invention are also useful as aids CROSS REFERENCE oRELATED APPLICATIONS for dispersing solid particles in organic liquids.They are especially useful as aids for dispersing pigments in Thisappllcatlon is a Continuation-impart of PP organic liquids. Illustrativeof the pigments which can lion 776,824, filed 13, 1963 now aban' bedispersed are titanium dioxide, carbon black, zinc donedoxide, leadtitanate, potassium titanate, antimony oxide,

STATEMENT OF THE INVENTION lithopone, phthalocyanine blue, toluidinered, quinacridone and the like. ThJS invention relates to polyesters. It1s more par- Pigment dispersions made with polymers of the tlcularlydlrected to polyesters represented y the struc vention are remarkablyresistant to flocculation, which tures gives the paints into which thedispersions are incor- (I) o porated higher initial gloss, better hidingand tinting strength, and makes them resistant to color drift and 7: Agloss loss. These pigment dispersions can also be used satisfactorilywith many more diverse types of paints and than conventional pigmentdispersions. Moreover, a 1 dispersion made with a polymer of theinvention has a (2) I f 0 significantly higher pigment content, whileretaining the R-AOY0i J-X-i J 0D same degree of fluidity, than whenconventional aids are used.

The polymers of the invention can be used as pigment dispersing aids bydissolving from 0.001 to about 2.00 R can be the residue from a p y y ycompound; grams of polymer per square meter 1 of surface of the A can bepigment to be used, preferably 0.004 to about 0.100 gram per squaremeter, in an organic liquid compatible with O o 0 0 the paint into whichthe pigment dispersion is to be A] g EL incorporated. Illustrative oforganic liquids which can T be used are aliphatic and aromatichydrocarbons, ethers,

or esters, 'ketones, alcohols and mixtures of these. R An appropriateamount of pigment is then added to l R5 3 I where this solution, which.is then subjected to shear, as by sand-grinding or ball-milling, todeagglomerate and diswhere perse the pigment. This pigment dispersion ormill-base is R R R and R, can be hydrogen or COOH then added dlmctly I aB Z can be Polymers of the 1nvent1on preferred for use as pigmentdispersing aids are those of formulas where R is 0 1|; 65 l)..- -CH S,0, or SO 12 X can be phenylene or an alkylene radical of 2 through CHTjO18 carbon atoms; Y can be an alkylene radical of 2 through 18 carbon Hatoms; D can be phenyl or a straightor branched chain alkyl radical ofthrough 18 carbon atoms; 1' Measured by the Brunauer, Emmett and Tellernitrogen a can b a number 2 h h 6; d adsorption method described on page30 of Colloidal Dispersions by Earl K. Fischer, published by John Wileyand n can be a number 10 through 500. s s in 1950,

CHaO- C-CHaO- CHzO Especially preferred are those polymers whosepreparation is shown in Examples 3, 4 and 5.

The polymers of the invention are also useful for dispersing magneticoxides such as iron oxide or chromium dioxide in compositions used toprepare magnetic tape. Use of 0.5-%, by weight of such a composition, ofa polymer of the invention promotes wetting of the oxide, improvesadhesion of the composition to the tape substrate and improves the tapesmagnetic properties.

PREPARATION OF THE POLYMERS The polymers of this invention are made byfirst reacting an anhydride with a polyol, and then reacting the productwith a hydroxyl terminated polyester.

Illustrative of anhydrides and polyols which can be used are trimelliticanhydride benzophenone dianhydride methylene diphthalic anhydridethiodiphthalic anhydride oxydiphthalic anhydride pyromelliticdianhydride ethylene glycol hexamethylene glycol glycerolpentaerythritol 4 hexanetriol dipentaerythritol diglycerol1,4-bishydroxymethyl benzene triethanolamine hexahydroxycyclohexane Theanyhydride and polyol are reacted by bringing together one anhydridemolecule for each hydroxyl group on the polyol and heating the reactionmass at 120-l50 C. for 2-5 hours. Ethylene glycol dimethyl ether canserve as a solvent if this is necessary.

The product is then reacted with a hydroxyl terminated polyester made byH CHa(CHz OH 3OHOCH2CH20H 301100 H OCH These reactions are described ingreater detail in Preparative Methods of Polymer Chemistry, Sorenson andCampbell, Interscience Publishers, Inc., New York, N.Y. (1961), pp.111-127 and 242-247 and Polyesters and Their Applications, BjorkstenResearch Laboratories, Inc., Reinhold Publishing Corp., New York, N.Y.(1956).

One mole of a polyester thus prepared for each anhydride group on theanhydride-polyol product is then reacted with that product at 120-150"C. for from 2 to 5 hours.

The resulting polymer of the invention can be isolated by stripping thesolvent from the resulting solution at C., at a pressure of 20 mm.

The physical properties of the polymers of the invention thus preparedrange from viscous liquid to friable solid. They are soluble in commonorganic liquids such as toluene, ethyl acetate, tetrahydrofuran,acetone, and dimethylformamide.

EXAMPLES The following examples are submitted so that the invention maybe more readily understood and practiced.

Those skilled in the art will no doubt be able to compose numerousvariations on their centraltheme, such as the attachment of innocuoussubstituents. It is naturally considered that these variations are apart of the invention.

In the examples all parts are by weight unless otherwise indicated.

Example 1 A mixture of pyromellitic dianhydride (43.6 parts), ethyleneglycol (6.6 parts) and anhydrous Cellosolve acetate (320 parts), washeated under nitrogen for three hours.

Exactly one-half of the product was heated with 296 parts of a hydroxylterminated polycaprolactone (molecular weight 2960) and 300 parts ofCellosolve acetate for 15 hours under nitrogen at 120 C. The solvent wasthen removed by stripping at 100 C. and 20 mm. of pressure to give awhite waxy solid having the structure Example 2 Example 3 A solution of50.7 parts of triethanolamine in 150 parts of methylethyl ketone wasadded to aslurry of 218 parts of pyromellitic dianhydride in 500 partsof methylethyl ketone. This mixture was heated at 40 C. for 3 hours andthen cooled to room temperature. The resulting solid was filtered offand dried under nitrogen.

Sixteen parts of the resulting product were mixed with 150 parts ofCellosolve acetate, added to 534 parts of a hydroxyl terminatedpolycaprolactone (molecular weight 2960) and heated under nitrogen forthree hours at C.

Solvent was removed by stripping at 100 C. and 20 mm. of pressure. Theproduct was a homogeneous waxy solid having the structure Example 4 v(A) A mixture of oxydiphthalic anhydride (18.7 parts),

dipentaerythritol (2.5 parts) and anhydrous ethylene glycol dimethylether (200 parts) was heated at C. for three hours and then cooled toroom temperature.

(B) One hundred sixty parts of 12-hydroxystearic acid, 7.8 parts of2-ethylhexyl alcohol, 10 parts of xylene and 1 part of p-toluenesulfonic acid were charged to a reactor. The reaction mixture was heatedat reflux and xylene distilled off until the flask contents reached C.The mixture was then refluxed at 175 C. for 8 hours, with water beingremoved as it formed.

The mixture was then cooled to about 100 C. and all of the product of(A) added. After heating the mixture for six hours at 100 C., themixture was freed of solvent by heating it at 100 C. and 20 mm. ofpressure for one hour. I

The product was a sticky resin having the structure M01120 crnoMMomo-c-omoom-o-cmorr MOHrO cmoM where M is COOH Example 5 where t t A Ris the residue from a polyhydroxy compound; (A) A mixture of methylenediphthalic anhydride (6.2 is i I v parts), 1,4-bis(hydroxymethyl)benzene (1.30 parts) and '6 1 R1 1 O anhydrous ethylene glycol dimethylether (100 parts) H I H e H was heated at 150 C. for three hours andthen cooled C -C --0 Z -C- to room temperature. t or i (B) Hexamethyleneglycol (47.2 parts), sebacic acid R4 R: R -R4' B R: g (80.8 parts),n-hexyl alcohol (2 parts), xylene parts) and p-toluene sulfonic acid (1part) were charged to a 10 2 vessel. The reaction mixture was heated atrefluxand where xylene distilled off until the temperature reached 150C. 7 R R R and R is hydrogen or COOl-I;V The mixture was then heated for10 hours at 150 C. Z is a 7 After cooling to 100 C., all of the productof A was 7 0 I 'added and the mixture heated six hours at 100 C, The

solvent was removed at 100 C. and mm. of pressure. g V v I The resultingsoft sticky solid had the structure I CH S-, --O'-, or SO 0 0H, e lo-l OJ-O(CHz OC /(CHa O(CHmCH; 5H L j /8 J20 cooH- 00011 7 n, on, o o 0-](5-0 -0(CH 0il(0H l )0 CH CH 3 L *7.- 1T .12., I COOH 00011 Example 6 Xis phenylene or an alkylene radical of 2 through 18 (A) A mixture ofpyromellitic dianhydride (2.18

parts) decamethylene glycol (1 part) and anhydrous Y is an alkyleneradical of 2 through 18 carbon atoms; ethylene glycol dimethyl ether (10Pal-ts) was heated D is phenyl or a straightor branched chain alkyl at150 C. for two hours and then cooled to room temradical of 1 through 18Carbon atoms; peratura 40 a is a number 2 through 6;

(B) Ethylene glycol 248 parts), adipic acid (584 and parts), dodecylalcohol (1.86 parts), xylene parts) 1S anumber 10 through V and P-Sulfollic acid (5 P Were charged to 2. The polymeric material of claim 1wherein R is a vessel. The mixture was heated at reflux and xylene 5 Vdistilled oil until the temperature reached 150 C. e 4 4 The mixture wasthen heated 10 hours at 150 C., with water being continuously removed.After. cooling to 2-12 100 C., all of (A) and 1000 parts of ethyleneglycol CH O dimethyl ether were added and the mixture heated six 50 2hours at 100 C. Solvent was removed by (heating the mixture at 100 C.and 20 mm. of pressure.

The resulting solid had the structure 0 0 0 o C--CHzO- l i -0 om)20 cm)li o (GHQ-on; I CHRO- I L 4 100 /n CH20 HOOG COOH CH O z 2):: H O (LH00C (COOK (in on CH 0 2 I 2 C -'CEO(CHZ)ZOC CHQ) (5 -0 (CH3 CH3 0 CH2CHIO 4 n g A g 0-1100 OCHz CCH OCH2C -CH2O- OCH CH 0- I claim: 1 2 1. Apolymeric material of the formula C1120- H(|7O 0 W n A- o-x-g oD] L llv. Y Z

0 o I' f u u\ :l HC O R-A-O-YOCXC-OD L In A 3. The polymeric material ofclaim 2 having the structure H000 COOH CH2() 4. The polymeric materialof claim 2 having the struc- 20 lure Q 0- MOHzC-C-CHaOCHz-C-CHzOM MOHzCCHZOM l 25 where M is CHZCHB 5. The polymeric material of claim 2 havingthe structure E fi E l E E1 Z; Q: o(0H, -o (011, owl-amen. I

' coorr- COOH COOH References Cited UNITED STATES PATENTS 2,422,3566/1947 Lasher 260-22 3,332,964 7/1967 McCracken et al. 260346.33,459,733 8/1969 Byrd et a1 260210 LEWIS GO'ITS, Primary Examiner D. G.RIVERS, Assistant Examiner US. Cl. X.R.

260-22 R, 76, 77, 470, 473 S, 404, 475 P, 78.3 R, 835, 850, 858, 860;106-266, 308 'R; 11716l, 167

